Nitrogenous derivatives of the anthraquinone series and process of making same



Patented Uni. 9, i934 stares NETRQGENUUS DERHVATEVES (BF THE AN- THRAQUINGNE SERIES AND IPRGJCESS @F Ii KAKHNG SAME Paul Gressrnann, Basel,

Switzerland, assignor to the firm of Society of (Chemical industry in Basie, Basel, Switzerland No Drawing. Application November 19, 1932, Serial Ne. 643,525. In Switzerland. December 7 Claims.

The present invention relates to the manufacture of new nitrogenous derivatives of the anthraquinone series. It comprises the process of making these new derivatives as well as the new derivatives themselves.

' monomethylarnine, monopropylaznine, monohydroxyethylamine, etc., referred to in the preceding paragraph to a temperature above 100 0., preferably in the presence of a small proportion of a reducing agent. The condensation can be carried out also with 1.45.B-tetrahydroxyanthraquinone in presence of a correspondingly larger proportion of the reducing agent. It-is a matter of course that also the leuco bodies of the 1.4- dihydroxy-5.S-diaminoanthraquinone or the alkyl derivatives thereof obtainable according to the above cited patents may be further condensed into the corresponding triamino-derivatives according to the present process. These leucobodies can be oxidized by known methods. The anthraquinone derivatives obtained are on the one hand valuable dyestufis for acetyl cellulose and on the other hand can in part be converted by sulfonation into wool dyestufis soluble in water. They correspond to the general formula NH I 1 1E wherein R represents H or alkyl. If R stands for alkyl the products are new. These new products constitute in a dry state dark powders which dissolve in organic solvents, such as acetic ester 'or alcohol, to blue to blue-green solutions.

The following examples illustrate the invention, the parts being by weight:-

Example 1 '27 parts of leuco-1.45.S-tetrahydroxyanthraquinone are heated in 250 parts of aqueous ame nionia solution of 2% per cent. strength with 3 parts of sodium hydrosulfite for 5 hours in a closed vessel at 120 C.; leuco-l-hydroxy-efifltriainincanthraquinone is produced and may be oxidized in the usual manner.

The l-hydroxy- L5.8-triaminoanthraquinone of the formula N112 0 OH NHS . yields on acetate sill; blue dyeings whichare of a blue as pure and as powerful as the dyeings obtained with l.45.8-tetraaminoanthraquinone, but exhibit, in contrast with the dyeings obtained with 1.45.8-tetraaminoanthraquinone an excellent fastness to light.

Example 2 I311 f NH O OH 1 II I IITHY NH CH3 CH which dissolves in acetic ester to a blue-green solution.

Example 3 25 parts of leuco-lA5.S-tetrahydroxyanthraquinone are heated in 150 parts or" water with 50 parts of 5-hydroxyethylamine and 4 parts of sodium hydrosulfite for 5 hours at 120 C. whereby, very probably, leuco-1hydroxy-4.5.8-trifihydroxyethylaminoanthraquinone is produced; this is worked up in the usual manner. By 0xidation there is very probably obtained the l-hydroxy 4.5.8-tri-p-hydroxyethylaminoanthraquinone of the formula HOCHzCHnNH (I? (1)11 HO CHzOHzNH O NHOHzOHaOH which dissolves in acetic ester to a blue-green solution.

Example 4 27 parts of pine leuco-1.4.5.8-tetrahydroxyanthraquinone are heated in 250 parts of aqueous manner.

following table wherein R stands for a member of the group of monovalent radicals consisting of H, CH3 and CHZOH, which products constitute dark powders which dissolve in acetic ester to blue-green solutions.

5. The anthraquinone derivatives of the general formula r NH (I? OH IYTH g IIIH alkyl alkyl which products constitute dark powders which dissolve in acetic ester to blue-green solutions.

6. The anthraquinone derivative of the formula 1.4.5.8-tetraaminoantliraquinone Iroduct according to the foregoing Example 1 ammonia solution of 24 per cent strength for 5 .hours in a closed vessel at 120 C.; leuco-l-hy- 0 OH droxy-4.5.8-triaminoanthraquinone is produced I I which may be isolated and oxidized in the usual Some features of the products obtained according to the foregoing examples and oxidized to g anthraquinone derivatives are exhibited in the NE NH a Ha Solution in Anthraquinone derivative Sulfuric acid-boric Sulfuric acid-[or- Summc acid acid maldchydo Colorless Colorless Violet. Yellow Yellowm Pure blue. Red-brown Violet Green. Yellow-brown R Pure blue. Red brown Green. Yellow-brown Pure blue.

Violet-red Green-blue Yellow-green.

What I claim is:

1. The manufacture of nitrogeneous derivatives of the anthraquinone series, consisting in heating leuco-l.45.8-tetrahydroxyanthraquinone at a temperature above 100 C. in an aqueous solution of bases of the group consisting of ammonia and primary aliphatic amines.

2. The manufacture of nitrogenous derivatives of the anthraquinone series, consisting in heating leuco-1.4.5.8-tetrahydroxyanthraquinone at a temperature above 100 C. in an aqueous solution of ammonia.

3. The manufacture of nitrogenous derivatives of the anthraquinone series, consisting in heating leuco-l.4.5.8-tetrahydroxyanthraquinone at a temperature above 100 C. in an aqueous solution of ammonia, in presence of a small proportion of a reducing agent.

4. The anthraquinone derivatives of the general formula CH R NH f) OH NH IIIH H R OHzR which product constitutes a dark powder which dissolves in acetic ester to a blue-green solution.

7. The anthraquinone derivative of the formula H0 CHZE H:

NH OH I NH 6 NH HOCH: H3 (IJHZOHZOH which product constitutes a dark powder which dissolves in acetic ester to a blue-green solution.

PAUL GROSSMANN. 

